Treatment of hydrocarbons



July 20, 1937.

J. 'A. GUYER TREATMENT oF HYDROCARBONS Filed Aug.. 11, 1934 Patented July 2o,y 1937 I 2,087,540

UNITED STATES PATENT oFFlcE TREATMENT F HYDROCARBONS Jesse A. Guyer, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Application 4August 11, 1934,- serial No. 739,498

4 claims. (o1. 19e-1o) This invention relates to the non-catalytic of 500 pounds per square inch. From the compolymerization of the simpler olen hydrocarbons pressor, the olen containing hydrocarbons pass into normally liquid hydrocarbons generally of through the heat exchanger 3, and the heating the gasoline boiling range. More specifically, it coil tinto the reaction chamber 5, entering there- 5 provides'an'improved and simplified process and in at a temperature on the order of 800 to 900 F., 5 apparatus whereby such polymerization may be or sufficient toA initiate the exothermicpolyeffected in a more economical and controllable merization reactions. Details of the reaction manner than is possible with processes heretofore chamber as shown in Figure 2 of the attached proposed for this purpose. drawingA will be later described.

The conversion of olen hydrocarbons into The gasesand polymers will usually leave the `10 polymeric molecules of higher molecular weight reaction chamber at a temperature of 40 F., or by the use of heat and pressure isa well known more above that of the entering gases, and pass reaction, and itsrexothermic character has also then through the lheat exchanger 3, the line l, been recognized. The present invention is a procand the pressure reduction valve 6 into the fracess wherein full advantage is taken ofthe tionator 8. Here unconverted and gaseous inate- 15 exothermic nature ofthe reaction to utilize the rials are separated as an overhead product, and heat evolved in the reaction to effect notable the normally liquid hydrocarbons are passed from economies in apparatus and equipment, while the bottom of the fractionator 8 into the fracconducting the reaction in a more controllable tionator 9`for separation into gasoline and tar.

manner and avoiding the excessive production of An essentiall feature of my process is'the pro- 20 tars and carbon such as are frequently encounvision of a reaction chamber wherein lindirect tered in cracking and polymerizing operations. heat exchange takes place between the incom- This is accomplished by the use of suitable heat ing gases and the olefines undergoing polyexchange equipment, preferably including a remerlzation.

action chamber designed to effectA indirect heat One form of apparatus suitable for this pur- 25 exchange between the incoming `and reactingl pose is shown in Figure 2 of the attached drawgases, as will be clear from the following descriping. Referring to this figure, the reaction chamtion'. ber comprises a housing A, preferably in the form Referring to the attached drawing, Figure '1 is of an elongated, cylindrical shell containing a a diagrammatic drawing of apparatus suitable number of spaced parallel tubes B longitudinally 30 for carrying out the process, including the necesarranged and connected to a common inlet header sary auxiliary equipment for separating the prod- C; with the other ends of the tubes open, the tubes ucts of theV process, whereas Figure 2 is a more terminating near' the opposite end of 'the chamdetailed drawing of a reaction chamber, such as vl'ier. The 'hydrocarbons preferably enter the that designated by the numeral 5 of Figure 1, chamber through the tubes Br flowing out the 35.

and representsone modication of apparatus open ends of the tubes in the far end Aof the rewherein the process may be carried out. action chamber, and returning along the outer An apparatus suitable for conducting my proc- Walls of the tubes to the point of exit, marked D ess is shown in Figure 1 of the attached drawon the drawing. Baillingmay be used within the 40 ing. The apparatus comprises a heat exchanger, shell if desired to make the vapors take an elon- 40 a reaction chamber in which the polymerization gated or spiral return course through the interis eifected,.atube coil with suitable housing for spaces between the tubes. Any liquid tar collectheating the hydrocarbons to be reacted and the 'ing in the reaction chamber is withdrawn through necessary pumps, piping and equipment for chargthe outlet E as required.

ingfraw stock to the process and separating the As used in the process, a temperature rise de- 45 eilluents of the reaction stage into normally liquid velops as a result of the reaction and heat is imhydrocarbons, and'unreacted gases, and further parted through the tube .walls to the incoming separating the liquid hydrocarbons into gasoline hydrocarbon within the tubes, raising the temand tar..' j. perature-of the incoming product suciently to In the operation of my process,`the charging initiate rapid'polymerization reactions, there be- 5o stock, containing a substantial proportion of oleing effected at, the same time a control of the iins of a molecular weight not exceeding approxireaction taking place in said interspaces by this mately 70, will be fed into the system through extraction of heat. The products from the polythe line l to the compressor 2 wherein they will merization vessel pass through the heat exbe compressed to a pressure preferably in excess changer where heat is imparted to the hydrocar- 55 lene, is suitable forconversion in the process.

The content of olens should in general be in excess of per cent of the hydrocarbon mixture but an olefin content of 30 per cent or more gives best results, there being no upper limit on the proportion of olefns in 'charging stock which may be' converted in the process. -at least 1000 pounds per square inch are desirable in order to take advantage of the heat exchange without the usual production of troublesome coke `and tar which may result from the high temperatures needed to eil'ect conversion at lower pressures, but higher pressures as high as 5000 pounds per square inch or even more may be used, the pressure being limited only by the strength ofthe apparatus. High pressures are in general benecial since they allow of the use' of the lower reaction temperatures.` Reaction temperatures between 700 and 1000 F. may be used but in most cases where an intermediate olefin content ,of 30-60 percent is present in the material under conversion, pressures of 200G-4000 pounds are used which are convenient fromthe standpoint of apparatus construction, and a temperature in the reaction chamber between t300-950 F. is preferable, the other temperatures in the system being adjusted so as'to maintain such a. temperature of reaction as will yield a maximum conversion of olens into polymers. A conversion of 6`5 to 80 per cent of the olefins present in the single thermal treatment is usually obtainable. A charging stock suitable for the process may be obtained from many sources provided only that the olen content is suiiiciently high and normally gaseous hydrocarbons predominate. Such a material may be obtained -from the cracking of normally gaseous hydrocarbons, from the catalytic dehydrogenation of parailins of low molecular weight or from the cracking of oil either at elevated pressures or low pressures, or from the destructive distillation of other bituminous materials. Concentrates of gaseous oleflns of high olen content, obtained by fractional distillation, are especially suitable. l

The apparatus shown in Figure 1 provides a novel method for starting the process with the small heating furnace provided. The tube coil, reaction chamber and conduits are i'llled with charging stock and charging stock is then forced by the pump through the heat exchanger, furnace coil and reaction chamber, the samematerial being then returned tothe inlet of the heat exchanger through the line I0 and the valve I I while heat is applied to the furnace coil, no more than a little hydrocarbon .being taken into or discarded from the apparatus during the heating, and the hydrocarbon passes several ktgirnes `through the heating coil, 'receiving each time an increment of heat. When the temperature has been raised suiiiciently to initiate exothermic conversion in Amic polymerization reaction, my process will pos- Operating pressures of sess decided advantages over those processes herey vsult of the exothermic natureof the conversion.

Having described my invention, what I claim is:l

1. A process for converting normally gaseous hydrocarbons containing a substantial proportion of oleiins -into normally liquid hydrocarbons, which comprises passing a charge of said hydrocarbons under pressure in excess of"500 pounds per square inch through a heat exchanger in indirect heat exchange relation with reaction products, passing said hydrocarbons from said heat exchanger through a tube coil in which an increment ofheat is imparted to said hydrocarbons, introducing said hydrocarbons from said tube coil into a reaction chamber through a plurality of confined passages, withdrawing said hydrocarbonsfrom said reaction chamber by causing said hydrocarbons to flow unrestrictedly about said conned passages to impart exothermic heat to said incoming hydrocarbonsrintroduced into said reaction chamber through said conned passages, withdrawing the reaction products .from

said reaction chamber and passing the same through said iirst mentioned heat exchanger in heat exchange relation with a charge of said hydrocarbons, and separating normally liquid hydrocarbons lfrom the said reaction products.

drocarbons to flow through a plurality of confined passages to the interior oi' said reaction chamber, withdrawing said hydrocarbons from said reaction chamber by causing the said hydrocarbons to flow unrestrictedly about said passages and to impart exothermic heat to said incoming hydrocarbons introduced to said reaction charnber through said conilned passages, withdrawing the reaction products from said reaction chamber and passing the same through said first mentioned heat exchanger in heat exchange rela-- tion with a charge of said hydrocarbons, andA separating normally liquid hydrocarbons from the said reaction products. l

3. A process for converting normally gaseous hydrocarbons containing a substantial proportion of oleilns into normally liquidhydrocarbons, which comprises passing said gaseous hydrocarbons through a heating zone to impart an increment of heat thereto, passing said hydrocarbons through one or more passageways oi' restricted cross-sectional area in a reaction zone whereinv said hydrocarbons are reacted with evolution of heat, and/conducting said reacted hydrocarbons' in indirect heat exchange relationship with said hydrocarbons entering the reaction zone and.

within the reaction zone.

4. A process for converting normally gaseous hydrocarbons containing a substantial proportion of olens into normally liquid hydrocarbons, which comprises passing said gaseous hydrocarbons under pressure in excess of 50D pounds per square inch through a heating zone to impart an increment of heat thereto, passing said hydrocarbons through one or more passageways in 

